Materials that react to external stimuli, for instances changes to their surrounding environments, have been the subject of significant research in view of the potential they offer to sectors of the economy as diverse as the medical, consumer-market, transportation, chemical and petrochemical sectors. For example, such an advanced material that would have the remarkable ability to degrade in order to actuate a well-defined function as a response to a change in its surrounding may be desirable because no or limited external human intervention would be necessary to actuate the function. Such a material, essentially self-actuated by changes in its surrounding (e.g., the presence or ingress of a specific fluid, or a change in temperature or pressure, among other possible changes) may potentially replace costly and complicated designs and may be most advantageous in situations where accessibility is limited or even considered to be impossible.
In a variety of subterranean and wellbore environments, such as hydrocarbon exploration and production, water production, carbon sequestration, or geothermal power generation, equipment of all sorts (e.g., subsurface valves, flow controllers, zone-isolation packers, plugs, sliding sleeves, accessories, etc) may be deployed for a multitude of applications, in particular to control or regulate the displacement of subterranean gases and liquids between subsurface zones. Some of these equipments are commonly characterized by relatively complex mechanical designs that are controlled remotely from the rig at ground level via wirelines, hydraulic control lines, or coil tubings.
Alternatively it may be desirable and economically advantageous to have controls that do not rely on lengthy and costly wirelines, hydraulic control lines, or coil tubings. Furthermore, in countless situations, a subterranean piece of equipment may need to be actuated only once, after which it may no longer present any usefulness, and may even become disadvantageous when for instance the equipment must be retrieved by risky and costly interventions. In such situations, the control or actuation mechanisms may be more conveniently imbedded within the equipment. In other applications, it may be beneficial to utilize the inherent ability of a material for reacting in the presence of an environmental change; for instance such a material may be applied to chemically sense the presence of formation water in a hydrocarbon well. In other foreseen applications, such a degradable material, if complemented by high mechanical strengths, may present new advantages in aquatic environments not only to withstand elevated differential pressures but also to control equipments deployed underwater with no or limited intervention.
In some instances, by way of example only, in the petroleum industry, it may be desirable to deploy a piece of equipment, apparatus, or device that performs a pre-determined function under differential pressures and then degrades such that the device no longer requires retrieval or removal by some method. By way of example only it may be advantageous to perform a multiple-stage oilfield operation such as that disclosed in U.S. Pat. No. 6,725,929. However, after the so-called ball, dart or plug is released in the wellbore to block gas and liquid transfers between isolated zones, it may be desirable to remove it by milling, flow-back, or alternate methods of intervention. In some instances, it may be simply more advantageous to manufacture equipments or devices, such as, by way of example only, balls, darts or plugs using a material that is mechanically strong (hard) and degrades under specific conditions, such as in the presence of water-containing fluids like fresh water, seawater, formation water, brines, acids and bases.
Unfortunately, the degradability of metallic materials, as defined by their lack of stability in a defined environment, as well as their ability to rapidly degrade (as opposed to the slow and uniform rusting or weight loss corrosion of steels for instance) may, in some instances, be accompanied with a number of undesirable characteristics. For example, among the very few metals that react and eventually fully degrade in water, both sodium metal and lithium metal, in addition to having low mechanical strengths, are water-reactive to the point they present great hazard along with great manufacturing, procurement, shipping and, handling challenges. Calcium metal is another reactive metal that in spite of being lesser reactive and slower to reacts than either sodium or lithium does not possess enough mechanical strength for normal engineering applications. Like sodium metal and lithium metal, calcium metal is thus unfit to many of the pressure-holding applications found for instances in the chemical and petroleum industries. When deficient, the properties of metals may be enhanced by alloying, meaning the chemical mixing of two or more metals and some other substances to form an end product, or alloy, with new properties that may be suitable for practical use. However, the alloying of lithium, sodium, or calcium metals with other metals and substances is not without major metallurgical and manufacturing challenges, and therefore the likelihood of creating an alloy with attractive engineering combinations of high strength, high toughness, and the proper degradability and rate of degradation (in a specific condition) is not only doubtful but also difficult to economically justify.
Table 1 compares several properties of pure metals with that of exploratory alloys in their annealed conditions (i.e., in the absence of cold working). Are listed in Table 1 measurements of hardness (Vickers hardness, as defined in the ASTM E370 standard) and galvanic corrosion potential, as simply established from voltage average readings of dissimilar metals and alloys electrically coupled by a aqueous electrolyte (here a sodium chloride enriched water). In this document, hardness and microhardness are considered to be fully interchangeable words; i.e., no distinction is made between the two words. Vickers hardness, or Vickers Microhardness, is a well-accepted and straight-forward measure that may be monotonically correlated to the mechanical strength of metals or alloys; e.g., the greater the hardness, the higher the mechanical strength of the material. Differently, galvanic corrosion potential is an electrochemical measure of reactivity, more precisely degradability, in an aqueous electrolytic environment, as produced by the coupling of materials with unlike chemical potentials. Though a low galvanic corrosion potential correlates to high degradability in water-containing fluid and often to high rates of degradation, rates of degradation are also influenced by other factors (e.g., water chemistry, temperature, pressure, and anode-to-cathode surface areas). Therefore, simplistically correlating rate of degradation to corrosion potential, despite being macroscopically correct as shown in Table 1, is not fully accurate for materials exhibiting especially comparable corrosion potentials. With these materials, factors such as temperature and water chemistry often have greater impacts on the rates of degradation than the galvanic corrosion potential itself. Galvanic corrosion potential and degradability may be considered purely as thermodynamic quantities, whereas rate of degradation is a kinetic quantity that is also influenced by other factors.
TABLE 1VickershardnessGalvanicnumbercorrosion(HVN)potential (Volts)*Aluminum metal (99.99 wt. %)33.3−0.60Magnesium metal (99.99 wt. %)32.5−0.90Calcium metal (99.99 wt. %)23.1−1.1280Al—10Ga—10In**33.4−1.4880Al—5Ga—5Zn—5Bi—5Sn**33.7−1.2875Al—5Ga—5Zn—5Bi—5Sn—5Mg**40.0−1.3865Al—10Ga—10Zn—5Bi—5Sn—5Mg**39.2−1.28*Galvanic corrosion potential was measured against a pure copper electrode (99.99 wt. %) in a 5 percent by eight sodium chloride aqueous solution; i.e., 5 wt. % NaCl in water.**All alloy compositions are listed in weight percent (wt. %); e.g. 80 wt. % Al—10 wt. % Ga—10 wt. % In.
Of all aluminum alloys, those referred as the “heat-treatable” alloys exhibit some of the most useful combinations of mechanical strength (hardness), impact toughness, and manufacturability; i.e., the ability to readily make useful articles of manufactures. These alloys are also characterized as being precipitation or age-hardenable because they are hardened or strengthened (the two words are interchangeable) by heat treatments that typically consist of three consecutive steps: (1) a solutionizing (solution annealing) heat-treatment for the dissolution of solid phases in a solid α-aluminum (α refers to pure aluminum's phase), (2) a quenching or rapid cooling for the development of a supersaturated α-aluminum phase at a given low temperature (e.g., ambient), and (3) an aging heat treatment for the precipitation either at room temperature (natural aging) or elevated temperature (artificial aging or precipitation heat treatment) of solute atoms within intra-granular phases. During aging, the solute atoms that were put into solid solution in the α-aluminum phase at the solutionizing temperature and then trapped by the quench are allowed to diffuse and form atomic clusters within the α-aluminum phase. These clusters or ultra fine intra-granular phases result in a highly effective and macroscopic strengthening (hardening) that provides some of the best combinations of mechanical strength and impact toughness.
An important attribute of age-hardenable alloys is a temperature-dependent equilibrium solid solubility characterized by increasing alloying element solubility with increasing temperature (up to a temperature above which melting starts). The general requirement for age hardenability of supersaturated solid solutions involves the formation of finely dispersed precipitates during aging heat treatment. The aging must be accomplished not only below the so-called equilibrium solvus temperature, but below a metastable miscibility gap often referred as the Guinier-Preston (GP) zone solvus line. For the development of optimal mechanical properties, age-hardening alloys must therefore be heat-treated according to predetermined temperature vs. time cycles. Failures in following an appropriate heat-treatment cycle may result in only limited strengthening (hardening); however any strengthening (hardening) would still be evidence of an aging response. The presence of age-hardening novel aluminum alloys that possess the unusual ability to degrade in water-containing fluids is a large part of the alloys disclosed herein.